Monoazo compounds containing long-chain alkyl radicals

ABSTRACT

Compounds of the formulae I and II ##STR1## in which A is a radical of the formulae III, IV or V ##STR2## R 1  and R 4  are --H or --Cl, R 2  and R 5  are --H, halogen, --NO 2 , --CN, C 1  -C 4  -alkyl, C 1  -C 4  alkoxy, --CF 3  or phenyloxy which is unsubstituted or substituted by one or two chlorine atoms and/or one or two methyl or methoxy groups, and R 3  is alkyl having at least 10 C atoms, X is a radical of the formulae --NH--, --O--, ##STR3## n is the number 1 or 2, Y is the radical of the formulae --COO--, --OOC--, --CONH-- or --NHCO-- or a radical of the formulae ##STR4## in which R 1  and R 2  are as defined above, D is an aromatic heterocyclic 5- or 6-membered ring, in which the ring contains 1 or 2 N atoms and may additionally contain an O atom or S atom, Z is --H, --Br, --OCH 3 , --CN or --NO 2  and X 1  and X 2 , independently of one another, are --H, halogen, --CH 3 , --OCH 3 , --OC 2  H 5  or --NO 2  and X 3  is --H, --NHCO--C 1  -C 4  alkyl, benzoylamino or phenylcarboxamide which are each unsubstituted or substituted on the phenyl ring by one or two chlorine atoms and/or one or two methyl or methoxy groups or an --NHCO--C 1  -C 4  alkyl group, or X 2  and X 3  together with the carbon atom to which they are bound are an aromatic carbocyclic 6-membered ring or an aromatic heterocyclic 5- or 6-membered ring, in which the heterocyclic ring contains 1 or 2 N atoms and can additionally have an O atom or S atom, and Y 1  is --H, --OCH 3 , --OC 2  H 5  or --NHCOCH 3 , with the proviso that X 3  must not be H, if X is --O-- or --NH--, are highly suitable for the mass coloration of plastics, in particular of polyolefins.

The present invention relates to novel monoazo compounds containing atleast one long-chain alkyl radical and their use for the dyeing ofplastics, in particular of polyolefins, in the mass.

Azo pigments which contain alkyl radicals have been known for a longtime. Red monoazo pigments are described, for example, in U.S. Pat. No.3,124,565 and in GB Patent No. 1,238,896 (based on2,3-oxynaphthoylaminobenzimidazolone) and in U.S. Pat. No. 4,229,344,U.S. Pat. No. 4,392,999 and U.S. Pat. No. 3,113,938 (based on2,3-oxynaphthoheteroarylide), while yellow monoazo compounds aredisclosed, for example, in U.S. Pat. No. 3,096,321 (based onacetoacetylaminobenzene), U.S. Pat. No. 3,555,002, U.S. Pat. No.3,555,003 and U.S. Pat. No. 4,150,019 (based onacetoacetylaminobenzimidazolone). The main characteristic of thecompounds listed there is that they have at least one lower alkylradical of 6 C atoms at most. The products described there have beenproposed for the pigmenting of plastics and paints. It is true that theyhave in general good pigment properties, but they do not always meettoday's requirements of industry, in particular with respect todispersability in certain applications.

Furthermore, according to German Offenlegungsschrift No. 3,634,393, itis known to use azo dyes which have carboxyl functions as solvent dyesfor the dyeing of film-forming polymers, such as cellulose acetates,nitro- and ethylcellulose, polyvinyl chloride, polyvinylbutyral,shellac, modified rosin, polyamide or polyacrylic acid resins. Theircarboxyl functions are alkylamide and/or alkyl ester radicals in whichthe sum of the C atoms in the ester and/or amide groups of the moleculeis greater than 8. Dyes of this type are distinguished by very highsolubility in the organic hydroxyl-containing solvents, such as are usedin the dyeing of the above-mentioned polymers.

Finally, Swiss Patent No. 329,048 describes fat-soluble azo dyes whichare derived, for example, from a naphthol AS component and contain along-chain carboxylic alkyl ester radical of, for example, 18 C atoms inthe diazo component.

It has now been found that monoazo pigments containing at least onelong-chain alkyl radical are surprisingly highly suitable for the masscolouration of plastics, in particular of polyolefins. These pigmentshave excellent dispersability, little tendency for efflorescence andgood general pigment properties.

The present invention accordingly relates to compounds of the formulae Iand II ##STR5## in which A is a radical of the formulae III, IV or V##STR6## R₁ and R₄ are --H or --Cl, R₂ and R₅ are --H, halogen, --NO₂,--CN, C₁ -C₄ -alkyl, C₁ -C₄ alkoxy, --CF₃ or phenyloxy which isunsubstituted or substituted by one or two chlorine atoms and/or one ortwo methyl or methoxy groups, and R₃ is alkyl having at least 10 Catoms, X is a radical of the formulae --NH--, --O--, ##STR7## n is thenumber 1 or 2, Y is the radical of the formulae --COO--, --OOC--,--CONH-- or --NHCO-- or a radical of the formulae ##STR8## in which R₁and R₂ are as defined above, D is an aromatic heterocyclic 5- or6-membered ring, in which the ring contains 1 or 2N atoms and mayadditionally contain an O atom or S atom, Z is --H, --Br, --OCH₃, --CNor --NO₂ and X₁ and X₂, independently of one another, are --H, halogen,--CH₃, --OCH₃, --OC₂ H₅ or --NO₂ and X₃ is --H, --NHCO-C₁ -C₄ alkyl,benzoylamino or phenylcarboxamido which are each unsubstituted orsubstituted on the phenyl ring by one or two chlorine atoms and/or oneor two methyl or methoxy groups or an --NHCO-C₁ -C₄ alkyl group, or X₂and X₃ together with the carbon atom to which they are bound are anaromatic carbocyclic 6-membered ring or an aromatic heterocyclic 5- or6-membered ring, in which the heterocyclic ring contains 1 or 2N atomsand can additionally have an O atom or S atom, and Y₁ is --H, --OCH₃,--OC₂ H₅ or --NHCOCH₃, with the proviso that X₃ must not be H, if X is--O-- or --NH--.

The formulae shown above represent one of the possible tautomeric forms.

Halogen in the groups listed above is fluorine, bromine and inparticular chlorine. C₁ -C₄ alkyl as R₂ and R₅ or in X₃ radicals--NHCO-C₁ -C₄ alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl and tert-butyl, but in particular methyl.

C₁ -C₄ alkoxy as R₂ and R₅ is, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy and tert-butoxy, but in particular methoxy.

X is preferably --O-- or --NH--, Y is preferably --COO-- or --CONH-- andn is preferably the number 1.

Z is preferably --H.

Aromatic carbocyclic 6-membered rings (in the definition of X₂ and X₃together with the carbon atoms of the adjacent phenyl ring) which aresuitable according to the invention are derived, for example, fromα-naphthlyamine.

Aromatic heterocyclic 5- or 6-membered rings (in the definition of X₂and X₃) which are suitable according to the invention are derived, forexample, from amines of the formula ##STR9## in which X₂ and X₃ form, asdefined, an aromatic heterocyclic 5- or 6-membered ring. Examples ofthese are: 5-amino-benzimidazolone, 7-chloro-5-amino-benzimidazolone,7-bromo-5-amino-benzimidazolone, 6-chloro-5-amino-benzimidazolone,6-bromo-5-amino-benzimidazolone, 6-methoxy-5-amino-benzimidazolone,7-methoxy-5-amino-benzimidazolone, 6-ethoxy-5-amino-benzimidazolone,7-chloro-4-methyl-5-amino-benzimidazolone,6-methyl-5-amino-benzimidazolone, 4,7-dimethyl-5-amino-benzimidazolone,4-methyl-6-chloro-5-amino-benzimidazolone,5-amino-1-methylbenzimidazolone, 6-amino-2,4-dihyroxyquinazoline,6-amino-1,4-dihydroxyquinazoline, 6-amino-4-methyl-2-quinolone,7-amino-4-methyl-2-quinolone, 7-amino-4,6-dimethyl-2-quinolone,6-amino-7-chloro-4-methyl-2-quinolone,7-amino-4-methyl-6-methoxy-2-quinolone, 5-aminobenzoxazolone,6-aminobenzoxazolone, 6-amino-5-methyl-benzoxazolone,6-amino-5-chloro-benzoxazolone, 6-amino-3-phenmorpholone,7-amino-6-chloro-3-phenmorpholone, 7-amino-6-methyl-3-phenmorpholone,7-amino-6-methoxy-3-phenmorpholone, 6-amino-4-methyl-3-phenmorpholone,7-amino-4-methyl-3-phenmorpholone,7-amino-4,6-dimethyl-3-phenmorpholone, 6-amino-4-quinazolinone and5-aminophthalimide.

Preference is given to the benzimidazolone compounds, in particular to5-amino-benzimidazolone, 6-methyl-5-amino-benzimidazolone and5-amino-1-methyl-benzimidazolone.

Alkyl having at least 10 C atoms in the definition of R₃ is branched orstraight-chain alkyl, for example n-decyl, n-dodecyl, n-tridecyl,isotridecyl, n-tetradecyl (myristyl), n-pentadecyl, n-hexadecyl,1-methylpentadecyl, n-octadecyl, n-eicosyl, n-tetracosyl, n-hexacosyl,n-triacontyl and n-pentacontyl.

Alkyl as R₃ is preferably C₁₂ - to C₃₅ alkyl, in particular C₁₂ - to C₁₈alkyl, or mixtures thereof, and is derived, for example, from thealcohols known and freely available as alfols which are used as startingmaterials and contain essentially alkyl groups having the same number ofC atoms and being predominantly branched. The alkyl groups aredesignated here as "alfyl", for example alfyl-C₁₂, alfyl-C₁₄. Long-chainalkylamine radicals having at least 10 C atoms, which are used asstarting materials, are derived, for example from n-decyl-, lauryl-,myristyl- and stearylamine.

Preference is given to compounds of the formulae I and II in which R₃ isC₁₂ -C₃₅ alkyl, Y is --COO-- or --CONH--, n is the number 1, and R₁, R₂,R₄, R₅, A and D are as defined above.

Particular preference is given to compounds of the formulae VI and VII##STR10## in which X is --O-- or --NH--, R₁ is --H or --Cl, and R₂ is--Cl, --CH₃, --OCH₃, --OC₂ H₅ or --OC₆ H₅, A is a radical of the formulaIII in which Z is --H, X₁ and X₂, independently of one another, are --H,--Cl, --CH₃ or --OCH₃, and X₃ is --H, --NHCOCH₃, benzoylamino orphenylcarboxamido which are each unsubstituted or substituted by one ortwo chlorine atoms and/or one or two methyl or methoxy groups or by--NHCOCH₃, or X₂ and X₃ together with the carbon atom to which they arebound form a ring of the formulae ##STR11## and R₃ is C₁₂ -C₁₈ alkyl, inparticular C₁₈ alkyl, with the proviso that X₃ in formula VI must not be--H, if X is --O-- or --NH--.

Particular preference is given to compounds of the formulae VI and VIIin which R₁ is --H and R₂ is --Cl, --CH₃ or --OCH₃, and the group--COXR₃ (in formula VII) is in the p-position relative to group R₂.

Very particular preference is given to compounds of the formula VIII,##STR12## in which X is --O-- or --NH--, R₂ is --CH₃ is C₁₂ -C₁₈ alkyl,in particular C₁₈ alkyl, and X₁, X₂ and X₃ are as defined above. In theabove formula VIII, X₁ and X₂ are preferably --H, --Cl or --CH₃ and X₃is benzoylamino which is unsubstituted or substituted by --Cl or --CH₃.

Examples of compounds of the formula I have the formula ##STR13## andexamples of compounds of the formula II have the formula ##STR14## inwhich X is --O-- or --NH--, R₁ and R₄ are --H or --Cl, R₂ and R₅ are--Cl, --CH₃ or --OCH₃ and R₃ is C₁₂ -C₁₈ alkyl, X₁ and X₂, independentlyof one another, are --H, --Cl, --CH₃ or --OCH₃, and X₃ is --H,--NHCOCH₃, benzoylamino which is unsubstituted or substituted by one ortwo chlorine atoms and/or one or two methyl or methoxy groups or by--NHCOCH₃, or X₂ and X₃ together with the carbon atom to which they arebound form a ring of the formulae ##STR15## and D is a5-benzimidazolonyl, 5- or 6-benzoxazolonyl,6-(2,4-dihydroxy)quinazolinyl, 6- or 7-(4-methyl)quinolone-2-yl, 6- or7-phenmorpholone-3-yl or 6-quinazolone-4-yl radical.

Preference is given to compounds of the formulae IX and X in which X is--O-- or --NH--, R₁ is --H or --Cl, R₂ is --Cl, --CH₃ or --OCH₃ and R₃is C₁₂ -C₁₈ alkyl, X₁ and X₂, independently of one another, are --H,--Cl, --CH₃ or --OCH₃, and X₃ is --H, --NHCOCH₃, benzoylamino which isunsubstituted or substituted by one or two chlorine atoms and/or one ortwo methyl or methoxy groups or by --NHCOCH₃, or X₂ and X₃ together withthe carbon atom to which they are bound form a ring of the formulae##STR16##

Very particular preference is given to compounds of the formula IX inwhich X is --O-- or --NH--, R₁ is --H, R₂ is --CH₃, R₃ is C₁₂ -C₁₈alkyl, and X₂ and X₃ together with the carbon atom to which they arebound form a ring of the formulae ##STR17##

The compounds of the formula I can be prepared by processes known perse, for example:

(a) by condensation of 1 mol of a carboxylic acid halide, in particulara chloride, of the formula ##STR18## with an amine of the formula##STR19## in accordance with, for example, U.S. Pat. No. 4,689,403, orby condensation of a carboxylic acid halide, in particular chloride, ofthe formula ##STR20## with 1 mol of a long-chain alcohol R₃ -OH or anamine R₃ NH₂, for example in accordance with U.S. Pat. No. 4,065,448, or

(b) by diazotization of an amine of the formula ##STR21## followed bycoupling of the diazo component obtained with a coupling component ofthe formulae ##STR22## for example in accordance with U.S. Pat. No.4,003,886, in which the groups n, R₁ to R₃, Hal, X₁, X₂, X₃ and Z are asdefined above.

The condensation process according to the above scheme (a) isadvantageously carried out in the presence of an organic inert solventunder normal or elevated pressure, with or without catalyst. Examples ofsuitable solvents are toluene, chlorobenzene, dichlorobenzenes, such aso-dichlorobenzene, furthermore trichlorobenzenes, nitrobenzene ormixtures of aromatic and/or aliphatic solvents, such as ®Shellsols.

The compounds of the formulae I in which X is --O-- or --NH-- can alsobe prepared via a transesterification or amidation reaction, bytransesterifying or amidating a compound of the formula ##STR23## inwhich R is advantageously C₁ -C₃ alkyl, and the remaining radicals n, A,R₁ and R₂ are as defined above, by means of an alcohol of the formula R₃--OH or an amine of the formula R₃ --NH₂ by known processes to givecompounds of the formula I. R is methyl, ethyl, propyl or isopropyl.

The transesterification or amidation is advantageously carried outdirectly in an excess of the corresponding long-chain alcohol or amine,if appropriate in the presence of an organic solvent, for exampletoluene, xylenes, dichlorobenzenes, nitrobenzene, chloronaphthalene,anisole, ®Dowtherm, or ketones, such as cyclohexanone, at elevatedtemperature, for example in the boiling range of the solvent used, undernormal or elevated pressure, with or without catalysts. If catalysts areused, sulfuric acid, p-toluene sulfonic acid, methanesulfonic acid, LiH,LiNH₂, NaOCH₃, potassium tert-butoxide, tetraalkyl titanates, dibutyltinoxide or rare earths are suitable.

The compounds of the formula II can be prepared, for example, bydiazotizing an amine of the formula H₂ N--D and coupling the resultingdiazo component with a coupling component of the formula ##STR24## inwhich D, R₄, R₅, Y and R₃ are as defined above.

Most of the above coupling components are known intermediates. Only thecoupling components of the last-mentioned formula are still novel. Thecarboxylic acid halides based on β-oxynaphthoic acid and thecorresponding acids thereof are also novel intermediates. They can beobtained by known processes, for example in accordance with U.S. Pat.No. 4,689,403.

The invention accordingly also relates to compounds of the formulae XIand XII below: ##STR25## in which n is the number 1 or 2, R₁ and R₄ are--H or --Cl, R₂ and R₅ are --H, halogen, --NO₂, --CN, C₁ -C₄ alkyl, C₁-C₄ alkoxy, --CF₃ or phenyloxy which is unsubstituted or substituted byone or two chlorine atoms and/or one or two methyl or methoxy groups, R₃is alkyl having at least 10 C atoms, Z is --H, --Br, --OCH₃, --CN orNO₂, and T is --OH or halogen, X is a radical of the formulae --NH--,--O--, ##STR26## in which R₁ and R₂ are as defined above and Y is aradical of the formula --COO--, --OOC--, --CONH--, --NHCO--, ##STR27##in which R₁ and R₂ are as defined above.

Halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy and R₃ are as defined above. T ispreferably --OH or --Cl. Y is preferably --CONH-- or --COO--.

Preferred compounds according to formula XI have the formula XIII##STR28## in which R₁, R₂, R₃, X and T are as defined above.

Highly preferred compounds have the formula XIII in which R₁ is --H, R₂is --Cl, --CH₃ or --OCH₃, R₃ is C₁₂ -C₁₈ alkyl, X is --O-- or --NH-- andT is --OH or --Cl.

After their synthesis, the compounds of the formulae I and II areisolated as usual, for example by filtration. The filtered material iswashed, for example, with one of the solvents already mentioned aboveand then advantageously again with water. They are usually obtained inhigh yield and purity and can be used without further purification infinely divided form for the mass colouration of plastics, in particularof polyolefins.

If their purity and/or particle form and size is not yet satisfactory oroptimum for their use as pigments, the compounds according to theapplication can be further conditioned. Conditioning is understood tomean the preparation of a fine particle form and size which is optimumfor the application, for example by dry milling in the presence orabsence of salt, by milling in the presence of solvents or water or bysalt kneading or by a subsequent thermal solvent treatment.

Thermal solvent treatments can be carried out, for example, in organicsolvents, preferably in those which boil above 100° C.

It has been found that particularly suitable solvents are benzenessubstituted by halogen atoms, alkyl or nitro groups, such as toluene,chlorobenzene, o-dichlorobenzene, xylenes or nitrobenzene, alcohols,such as isopropanol or isobutanol, furthermore ketones, such ascyclohexanone, ethers, such as ethylene glycol monomethyl or monoethylether, amides, such as dimethylformamide or N-methylpyrrolidone and alsodimethyl sulfoxide, sulfolane or water alone, if appropriate underpressure. The aftertreatment can also be carried out in water in thepresence of organic solvents and/or with the addition of surface-activesubstances or aliphatic amines, or in liquid ammonia.

Depending on the conditioning process and/or intended application, itcan be advantageous to add certain amounts of texture-improving agentsbefore or after their conditioning process to the compound according tothe invention of the formulae I or II. Suitable compounds of this typeare in particular fatty acids having at least 18 C atoms, for examplestearic or behenic acid or amides or metal salts thereof, in particularMg salts. The texture-improving agents are preferably used in amounts of0.1-30% by weight, in particular 2-15% by weight, relative to the finalproduct.

However, due to their excellent compatibility with polyolefins, theresulting compounds according to the invention of the formulae I and IIcan often be incorporated direct into polyolefins, for the purpose ofcolouration, without any further conditioning such as mechanicalcomminution or preparation.

Although they are in particular suitable for the mass colouration ofpolyolefins, they can also advantageously be used for the masscolouration of other polymers, for example polyvinyl chloride, but inparticular for the colouration of engineering plastics, for examplepolycarbonates, polyacrylates, polymethacrylates, ABS, polyesters,polyamides, polyether ketones, polyurethanes, individually or inmixtures. Advantageously, they are used in a concentration of 0.01 to 5%by weight, relative to the polymer.

Examples of polyolefins which can be coloured by means of the compoundsaccording to the invention of the formulae I and II are polyethylene ofhigh and low density (HDPE, LDPE and LLDPE), polypropylene andpolyisobutylene, and copolymers of polyolefins with, for example,polyethers, polyether ketones or polyurethanes.

The colouration is carried out by conventional processes, for example bymixing a compound of the formulae I or II with the plastic granules orpowder and extruding the mixture to give fibres, sheets or granules. Thelatter can then be moulded to articles by injection-moulding.

The colourations obtained have high purity and high saturation and aredistinguished by good resistance, in particular to heat and light, andby their low bleeding tendency. A particular advantage of polyethylenearticles coloured by means of the compounds according to the inventionof the formulae I and II is that they do not show, in particular in thecase of HDPE, any increased tendency for distortion and deformationphenomena.

The fibres coloured by means of the compounds according to the inventionof the formulae I and II have excellent textile properties, for examplelight and wet fastness properties towards detergents and solvents.

The Examples which follow serve to illustrate the invention.

EXAMPLE 1

4.05 g of stearyl 4-methyl-3-aminobenzoate and 3.8 g of4-benzoylamino-1-(2'-hydroxy-3'-naphthoylamino)benzene are dissolved ina mixture of 125 ml of glacial acetic acid and 125 ml ofN-methylpyrrolidone at 70° C. The clear red-brown solution is cooled to40° C., and 2.55 ml of a 4N sodium nitrite solution are added dropwiseat this temperature. A red precipitate is formed. The resulting redsuspension is stirred for another 6 hours. The product is then filteredoff with suction and washed with 300 ml of ethyl alcohol. After dryingin vacuo at 60° C., 7.2 g (90.5% of theory) of a deep red powder of theformula ##STR29## is obtained, which gives the following combustionanalysis (C₅₀ H₆₀ N₄ O₅): Calc. (in %): C 75.35 H 7.59 N 7.03; Found (in%): C 75.30 H 7.64 N 6.81.

This product which is aftertreated at 125° C. for 1 hour in ethyleneglycol monoethyl ether colours polyethylene in strong pure red hues ofexcellent heat and light resistance.

EXAMPLE 2 TO 51

In the Table below, further compounds are described, which are obtainedanalogously to the above Example 1 by coupling of the diazotized amineaccording to column I with a coupling component from column II. ColumnIII shows the hue of the PVC sheet coloured by means of the compoundsthus obtained. In the cases where the components of columns I and IIalready give a clear solution in glacial acetic acid of up to 80° C.,the addition of N-methylpyrrolidone can be omitted. Otherwise, theprocedure of Example 1 is followed.

    __________________________________________________________________________    Ex.                                                                              I                  II                    III                               __________________________________________________________________________    2  N-stearyl-4-methyl-3-amino-benz-                                                                 4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          scarlet                              amide              amino)-benzene                                          3  Stearyl-3-amino-benzoate                                                                         4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          orange                                                  amino)-benzene                                          4  Stearyl-4-chlor-3-amino-benzoate                                                                 4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          orange-                                                 amino)-benzene        red                               5  n-Decyl-4-methyl-3-amino-benzoate                                                                4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          cermine                                                 amino)-benzene                                          6  Lauryl-4-methyl-3-amino-benzoate                                                                 4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          red                                                     amino)-benzene                                          7  n-Tetradecyl-4-methyl-3-amino-benzoate                                                           4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          red                                                     amino)-benzene                                          8  Stearyl-4-methyl-3-amino-benzoate                                                                4-(4''-Chlorbenzoylamino)-1-(2'-hydroxy-3-                                                          red                                                     naphthoylamino)-benzene                                 9  Stearyl-4-methyl-3-amino-benzoate                                                                4-Benzoylamino-2,5-diethoxy-1-(2'-hydroxy-                                                          red-brown                                               3'-naphthoylamino)-benzene                              10 Stearyl-4-methyl-3-amino-benzoate                                                                4-(4''-Acetamino-benzoylamino)-1-(2'-hydroxy-                                                       red                                                     3'-naphthoylamino)-benzene                              11 Stearyl-4-methyl-3-(4'-methyl-3'-                                                                N-phenyl-2-hydroxy-3-naphthamide                                                                    red                                  amino-benzoylamino)-benzoate                                               12 N-stearyl-4-methyl-3-(4'-methyl-3'-                                                              N-phenyl-2-hydroxy-3-naphthamide                                                                    red                                  amino-benzoylamino)-benzamide                                              13 Stearyl-4-methyl-3-(4'-chlor-3'-amino-                                                           N-phenyl-2-hydroxy-3-naphthamide                                                                    scarlet                              benzoylamino)-benzoate                                                     14 Stearyl-4-chlor-3-(4'-chlor-3'-amino-                                                            N-phenyl-2-hydroxy-3-naphthamide                                                                    orange-                              benzoylamino)-benzoate                   red                               15 Stearyl-4-methyl-3-(4'-methyl-3'-                                                                4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          cermine                              amino-benzoylamino)-benzoate                                                                     amino)-benzene                                          16 N-stearyl-4-methyl-3-(4'-methyl-3'-                                                              4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          cermine                              amino-benzoylamino)-benzamide                                                                    amino)-benzene                                          17 Stearyl-4-methyl-3-(4'-chlor-3'-                                                                 4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          red                                  amino-benzoylamino)-benzoate                                                                     amino)-benzene                                          18 Stearyl-4-chlor-3-(4'-chlor-3'-amino-                                                            4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          scarlet                              benzoylamino)-benzoate                                                                           amino)-benzene                                          19 N-stearyl-4-methyl-3-amino-benzamide                                                             4-(2'-Hydroxy-3'-naphthoylamino)-benzanilide                                                        red                               20 Stearyl-4-chlor-3-amino-benzoate                                                                 4-(2'-Hydroxy-3'-naphthoylamino)-benzanilide                                                        orange-                                                                       red                               21 Stearyl-4-methoxy-3-amino-benzoate                                                               4-(2'-Hydroxy-3'-naphthoylamino)-benzanilide                                                        cermine                           22 Stearyl-4-methyl-3-(4'-methyl-3'-                                                                4-(2'-Hydroxy-3'-naphthoylamino)-benzanilide                                                        red                                  amino-benzoylamino)-benzoate                                               23 N-stearyl-4-methyl-3-(4'-methyl-3'-                                                              4-(2'-Hydroxy-3'-naphthoylamino)-benzanilide                                                        red                                  amino-benzoylamino)-benzamide                                              24 Stearyl-4-methyl-3-(4'chlor-3'-amino-                                                            4-(2'-Hydroxy-3'-naphthoylamino)-benzanilide                                                        red                                  benzoylamino)-benzoate                                                     25 Stearyl-4-chlor-3-(4'-chlor-3'-amino-                                                            4-(2'-Hydroxy-3'-naphthoylamino)-benzanilide                                                        scarlet                              benzoylamino)-benzoate                                                     26 Stearyl-4-methyl-3-amino-benzoate                                                                5-(2'-Hydroxy-3'-naphthoylamino)-6-methyl-                                                          red-brown                                               benzimidazolone                                         27 N-stearyl-4-methyl-3-amino-benzamide                                                             5-(2'-Hydroxy-3'-naphthoylamino)-6-methyl-                                                          red-brown                                               benzimidazolone                                         28 Stearyl-4-methyl-3-amino-benzoate                                                                5-(2'-Hydroxy-3'-naphthoylamino)-6-chlor-                                                           red-brown                                               benzimidazolone                                         29 Stearyl-4-methyl-3-amino-benzoate                                                                6-(2'-Hydroxy-3'-naphthoylamino)-4-methyl-                                                          red-brown                                               7-chlor-2-quinolone                                     30 Stearyl-4-methyl-3-amino-benzoate                                                                7-(2'-Hydroxy-3'-naphthoylamino)-phen-3-                                                            red-brown                                               morpholone                                              31 Stearyl-4-methyl-3-amino-benzoate                                                                6-(2'-Hydroxy-3'-naphthoylamino)-2-methyl-4-                                                        red-brown                                               quinazolone                                             32 Stearyl-4-methyl-3-amino-benzoate                                                                5-(2'-Hydroxy-3'-naphthoylamino)-7-chloro-                                                          red-brown                                               benzimidazolone                                         33 Stearyl-4-methyl-3-(4'-methyl-3'-                                                                5-(2'-Hydroxy-3'-naphthoylamino)-1-methyl-                                                          red                                  amino-benzoylamino)-benzoate                                                                     benzimidazolone                                         34 Stearyl-4-methyl-3-(4'-chloro-3'-                                                                5-(2'-Hydroxy-3'-naphthoylamino)-1-methyl-                                                          red                                  amino-benzoylamino)-benzoate                                                                     benzimidazolone                                         35 Stearyl-4-chloro-3-(4'-chloro-3'-                                                                5-(2'-Hydroxy-3'-naphthoylamino)-1-methyl-                                                          red                                  amino-benzoylamino)-benzoate                                                                     benzimidazolone                                         36 N-stearyl-4-methyl-3-amino-benzamide                                                             6-Acetoacetylamino-benzimidazolone                                                                  yellow                            37 Stearyl-4-methyl-3-amino-benzoate                                                                1-Methyl-5-acetoacetylamino-benzimidazolone                                                         yellow                            38 n-Decyl-4-amino-benzoate                                                                         6-Acetoacetylamino-benzimidazolone                                                                  yellow                            39 Lauryl-4-methyl-3-amino-benzoate                                                                 6-Acetoacetylamino-benzimidazolone                                                                  yellow                            40 n-Tetradecyl-4-methyl-3-amino-benzoate                                                           6-Acetoacetylamino-benzimidazolone                                                                  yellow                            41 Stearyl-4-methyl-3-(4'-methyl-3'-                                                                6-Acetoacetylamino-benzimidazolone                                                                  yellow                               amino-benzoylamino)-benzoate                                               42 Stearyl-4-methyl-3-(4'-chloro-3'-                                                                6-Acetoacetylamino-benzimidazolone                                                                  yellow                               amino-benzoylamino)-benzoate                                               43 Stearyl-4-chloro-3-(4'-chloro-3'-                                                                6-Acetoacetylamino-benzimidazolone                                                                  green-                               amino-benzoylamino)-benzoate             yellow                            44 5-Amino-6-chloro-benzimidazolone                                                                 Stearyl-3-acetoacetylamino-4-methyl-                                                                green-                                                  benzoate              yellow                            45 Stearyl-anthranilate                                                                             4-Acetoacetamino-acetanilide                                                                        yellow                            46 Stearyl-anthranilate                                                                             6-Acetoacetylamino-benzimidazolone                                                                  yellow                            47 Stearyl-anthranilate                                                                             5-Acetoacetylamino-6-chlorbenzimidazolone                                                           yellow                            48 Stearyl-anthranilate                                                                             1-Methyl-5-acetoacetylamino-benzimidazolone                                                         yellow                            49 N-stearylanthranilamide                                                                          6-Acetoacetylamino-benzimidazolone                                                                  yellow                            50 N-stearylanthranilamide                                                                          1-Methyl-5-acetoacetylamino-benzimidazolone                                                         yellow                            51 N-stearyl-4-methyl-3-amino-benzamide                                                             1-(2'-Hydroxy-3'-naphthoylamino)-naphthalene                                                        cermine                           52 Stearyl-anthranilate                                                                             4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          scarlet                                                 amino)-benzene                                          53 Stearyl-anthranilate                                                                             4-(2'-Hydroxy-3'-naphthoylamino)-benzo-4''-                                                         red                                                     toluidide                                               54 Stearyl-anthranilate                                                                             4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          scarlet                                                 amino)-benzene                                          55 N-stearyl-anthranilamide                                                                         4-Benzoylamino-1-(2'-hydroxy-3'-naphthoyl-                                                          red                                                     amino)-benzene                                          56 Lauryl-anthranilate                                                                              5-(2'-Hydroxy-3'-naphthoylamino)-benz-                                                              red-                                                    imidazolone           brown                             57 Lauryl-anthranilate                                                                              5-(2'-Hydroxy-3'-naphthoylamino)-6-methyl-                                                          brown                                                   benzimidazolone                                         58 Stearyl-anthranilate                                                                             5-(2'-Hydroxy-3'-naphthoylamino)-benz-                                                              red-                                                    imidazolone           brown                             59 Stearyl-anthranilate                                                                             5-(2'-Hydroxy-3'-naphthoylamino)-benz-                                                              red-                                                    imidazolone           brown                             60 Stearyl-anthranilate                                                                             5-(2'-Hydroxy-3'-naphthoylamino)-1-methyl-                                                          red                                                     benzimidazolone                                         __________________________________________________________________________

EXAMPLE 61

12.4 g of the azo dye from diazotized stearyl 4-methoxy-3-aminobenzoateand 2-hydroxy-3-naphthoic acid are suspended in 120 ml of anhydroustoluene. 2 ml of thionyl chloride and 4 drops of dimethylformamide areadded to the mixture, which is then heated at 80° C. with stirring forone hour and 15 minutes. The bordeaux-coloured solution is completelyevaporated in vacuo. The product obtained is then removed from the flaskby means of 50 ml of petroleum ether, filtered off with suction, anddried at 50° C. in vacuo. This gives 12.2 g (95.7% of theory) of the azocarbonyl chloride of the formula ##STR30## and melting point 129° to130° C.

Combustion analysis: Calc.: C 69.74 H 7.75 Cl 5.56 N 4.40% Found: C69.66 H 7.75 Cl 5.65 N 4.22%

6.4 g of the azo carbonyl chloride thus prepared are stirred with 100 mlof N-methylpyrrolidone, and the mixture is heated to 60° C. At thistemperature, 1.6 g of 5-amino-1-methylbenzimidazolone are added to theclear black solution, resulting in a thick red suspension, which isheated to 92° C. with stirring and stirred at this temperature for 7hours. The suspension is cooled to room temperature and diluted with 60ml of ethanol. The product is finely filtered off with suction andwashed with 200 ml of ethanol. Drying of the product at 60° C. in vacuogives 7.2 g (94% of theory) of a red powder in the form of softgranules, which colours, for example, polyethylene, polyamide andpolyvinyl chloride in strong red hues which have good heat and lightresistance.

The formula of the product obtained: ##STR31##

Combustion analysis: Calc.: C 70.75 H 7.52 N 9.17% Found: C 70.78 H 7.64N 9.11%

The Table below contains further pigments, which can be prepared by theprocess of the above Example 61 by coupling the diazo compound of one ofthe amines listed in column I on to 2-hydroxy-3-naphthoic acid,subsequently converting the azo carboxylic acid obtained into thecorresponding acid chloride, which is condensed with one of the amineslisted in column II. Column III lists the hue of the polyvinyl chloridesheet coloured by means of the pigments obtained.

    ______________________________________                                        Ex.  I            II                III                                       ______________________________________                                        62   Stearyl-4-methyl-                                                                          5-Amino-1-methyl-benzimi-                                                                       red                                            3-amino-benzoate                                                                           dazolone                                                    63   Stearyl-4-methyl-                                                                          5-Amino-benzimidazolone                                                                         red-                                           3-amino-benzoate               brown                                     64   Stearyl-2-amino-                                                                           5-Amino-6-methyl-benzimi-                                                                       yellow-                                        terephthalate                                                                              dazolone          brown                                     65   Stearyl-3-amino-                                                                           5-Amino-1-methyl-benzimi-                                                                       red                                            benzoate     dazolone                                                    66   Stearyl-4-chloro-                                                                          5-Amino-1-methyl-benzimi-                                                                       orange-                                        3-amino-benzoate                                                                           dazolone          red                                       67   n-Decyl-4-methyl-                                                                          5-Amino-1-methyl-benzimi-                                                                       red                                            3-amino-benzoate                                                                           dazolone                                                    68   Lauryl-4-methyl-                                                                           5-Amino-1-methyl-benzimi-                                                                       red                                            3-amino-benzoate                                                                           dazolone                                                    69   n-Tetradecyl-4-                                                                            5-Amino-1-methyl-benzimi-                                                                       red                                            methyl-3-amino-                                                                            dazolone                                                         benzoate                                                                 ______________________________________                                    

EXAMPLE 70

A mixture of 1.0 g of the product obtained according to Example (1) 1.0g of antioxidant (®IRGANOX 1010, CIBA-GEIGY AG) and 1000 g ofpolyethylene HD granules (®VESTOLEN A 60-16, HUELS) is premixed in a 3 lglass bottle on a roller stand for 15 minutes. The mixture is thenextruded twice through a single-screw extruder and then granulated. Thegranules thus obtained are then injection-moulded on aninjection-moulding machine (®Allround Arburg 200) at 220° C., 250° C.and 300° C. at a residence time of 5 minutes each to give sheets. Thesheets thus obtained have uniformly strong red colourations and are asdistortion-free as moulded material of uncoloured polyethylene. If themoulded sheets thus coloured are left in an oven at 100° C. for 24hours, no bleeding of the pigment from the plastic can be observed.

EXAMPLE 71

The procedure as described in Example 70 is repeated, except that 10 gof titanium dioxide ®KRONOS RN 57-P (KRONOS Titan GmbH) are used inaddition to the coloured pigment. Red pressed sheets are obtained whichhave the same heat resistances. The pressed sheets moulded between 200°and 300° C. do not show colour changes after cooling.

EXAMPLE 72

1000 g of polypropylene granules (®DAPLEN PT-55, Chemie LINZ) and 1.0 gof the product obtained according to Example (1) are mixed in a 3 lbottle on a roller stand for 15 mintures. The mixture is then extrudedtwice through a single-screw extruder and then granulated. The granulesthus obtained are spun at 280°-285° C. by the melt-spinning process. Thefibres thus coloured have very good light resistance and excellenttextile fastness properties, such as rub fastness and wet fastnesstowards detergents and solvents. The heat resistance at 285° C. isexcellent.

EXAMPLE 73

100 g of polymethyl methacrylate granules (®DEGALAN 7E from DEGUSSA AG)and 0.2 g of the product obtained according to Example (1) are premixedin a 500 ml glass bottle on a roller stand for 20 minutes. The mixtureis then extruded on a single-screw extruder to give a tape. Atransparent strongly red-coloured plastic tape is obtained which hasexcellent heat and light resistances.

EXAMPLE 74

The procedure as described in Example 73 is repeated, except thatpolycarbonate granules (®MAKROLON 2800 from BAYER) are used instead ofpolymethyl methacrylate, to give transparent deep red tapes which haveexcellent heat and light resistances.

What is claimed is:
 1. A compound of the formulae I or II ##STR32## inwhich A is a radical of the formulae III, IV or V ##STR33## R₁ and R₄are --H or --Cl, R₂ and R₅ are --H, halogen, --NO₂, --CN, C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy, --CF₃ or phenyloxy which is unsubstituted or substitutedby one or two chlorine atoms, one or two methyl or methoxy groups, or byone or two chlorine atoms and one or two methyl or methoxy groups and R₃is alkyl having at least 10 C atoms, X is a radical of the formulae--NH--, --O--, ##STR34## n is the number 1 or 2, Y is the radical of theformulae --COO--, --OOC--, --CONH-- or --NHCO-- or a radical of theformulae ##STR35## in which R₁ and R₂ are as defined above, D is a5-benzimidazolonyl, 5- or 6-benzoxazolonyl,6-(2,4-dihydroxy)-quinazolinyl, 6- or 7-(4-methyl)quinolone-2-yl, 6- or7-phenmorpholone-3-yl or 6-quinazolone-4-yl radical, Z is --H, --Br,--OCH₃, --CN or --NO₂ and X₁, and X₂, independently of one another, are--H, halogen, --CH₃, --OCH₃ --OC₂ H₅ or --NO₂ and X₃ is --H, --NHCO--C₁-C₄ -alkyl, benzoylamino or phenylcarboxamido which are eachunsubstituted or substituted on the phenyl ring by one or two chlorineatoms, one or two methyl or methoxy groups, one or two chlorine atomsand one or two methyl or methoxy groups, or an --NHCO--C₁ -C₄ alkylgroup, or X₂ and X₃ together with the carbon atom to which they arebound are an aromatic carboxylic 6-membered ring or an aromaticheterocyclic 5- or 6-membered ring selected from the group consisting of5-amino-benzimidazolone, 7-chloro-5-amino-benzimidazolone,7-bromo-5-amino-benzimidazolone, 6-chloro-5-amino-benzimidazolone,6-bromo-5-amino-benzimidazolone, 6-methoxy-5-amino-benzimidazolone,7-methoxy-5-amino-benzimidazolone, 6-ethoxy-5-amino-benzimidazolone,7-chloro-4-methyl-5-amino-benzimidazolone,6-methyl-5-amino-benzimidazolone, 4,7-dimethyl-5-amino-benzimidazolone,4-methyl-6-chloro-5-amino-benzimidazolone,5-amino-1-methyl-benzimidazolone, 6-amino-2,4-dihydroxyquinazoline,6-amino-1,4-dihydroxyquinazoline, 6-amino-4-methyl-2-quinolone,7-amino-4-methyl-2-quinolone, 7-amino-4,6-dimethyl-2-quinolone,6-amino-7-chloro-4-methyl-2-quinolone,7-amino-4-methyl-6-methoxy-2-quinolone, 5-aminobenzoxazolone,6-amino-benzoxazolone, 6-amino-5-methyl-benzoxazolone,6-amino-5-chloro-benzoxazolone, 6-amino-3-phenmorpholone,7-amino-6-chloro-3-phenmorpholone, 7-amino-6-methyl-3-phenmorpholone,7-amino-6-methoxy-3-phenmorpholone, 6-amino-4-methyl-3-phenmorpholone,7-amino-4-methyl-3-phenmorpholone,7-amino-4,6-dimethyl-3-phenmorpholone, 6-amino-4-quinazolinone and5-aminophthalimide, and Y₁ is --H, OCH₃, --OC₂ H₅ or --NHCOCH₃, with theproviso that X₃ must not be H, if X is --O-- or --NH--.
 2. A compoundaccording to claim 1, in which X is --O-- or --NH--, Y is a radical ofthe formula --COO-- or --CONH-- and n is the number
 1. 3. A compoundaccording to claim 1, in which R₃ is C₁₂ -C₃₅ alkyl, Y is --COO-- or--CONH-- and n is the number
 1. 4. A compound according to claim 1,which has the formulae VI or VII ##STR36## in which X is --O-- or--NH--, R₁ is --H or --Cl, and R₂ is --Cl, --OCH₃, --CH₃, --OC₂ H₅ or--OC₆ H₅, A is a radical of the formula III according to claim 12 inwhich Z is --H, X₁ and X₂, independently of one another, are --H, --Cl,--CH₃ or --OCH₃, and X₃ is --H, --NHCOCH₃, benzoylamino orphenylcarboxamido which are each unsubstituted or substituted by one ortwo chlorine atoms, one or two methyl or methoxy groups, one or twochlorine atoms and one or two methyl or methoxy groups or by --NHCOCH₃,or X₂ and X₃ together with the carbon atom to which they are bound forma ring of the formulae ##STR37## and R₃ is C₁₂ -C₁₈ alkyl, with theproviso that X₃ in formula VI must not be --H, if X is --O-- or --NH--.5. A compound according to claim 4, in which R₁ is --H, R₂ is --Cl,--CH₃ or --OCH₃, and the group --COXR₃ in formula VII is in thepara-position relative to the group R₂.
 6. A compound according to claim4, which has the formula VIII ##STR38## in which X is --O-- or --NH--,R₂ is --CH₃ and R₃ is C₁₂ -C₁₈ alkyl.
 7. A compound according to claim1, which has the formula IX or X ##STR39## in which X is --O--, or--NH--, R₁ is --H or --Cl, R₂ is --Cl, --CH₃ or --OCH₃ and R₃ is C₁₂-C₁₈ alkyl, X₁ and X₂, independently of one another, are --H, --Cl,--CH₃ or --OCH₃, and X₃ is --H, --NHCOCH₃, benzoylamino which isunsubstituted or substituted by one or two chlorine atoms, one or twomethyl or methoxy groups, one or two chlorine atoms and one or twomethyl or methoxy groups or by --NHCOCH₃, or X₂ and X₃ together with thecarbon atom to which they are bound form a ring of the formula ##STR40##8. A compound of the formulae XI ##STR41## in which n is the number 1 or2, R₁ is --H or --Cl, R₂ is --H, halogen, --NO₂, --CN, C₁ -C₄ alkyl, C₁-C₄ alkoxy, --CF₃ or phenyloxy which is unsubstituted or substituted byone or two chlorine atoms, one or two methyl or methoxy groups, or oneor two chlorine atoms and one or two methyl or methoxy groups, R₃ isalkyl having at least 10 C atoms, Z is --H, --Br, --OCH₃, --CN or NO₂, Tis --OH or halogen and X is a radical of the formulae --NH--, --O--,##STR42##
 9. A compound according to claim 8, which has the formula XIII##STR43##
 10. A compound of the formula XIII according to claim 9, inwhich R₁ is --H, R₂ is --Cl, --CH₃ or --OCH₃, R₃ is C₁₂ -C₁₈ alkyl, X is--O-- or --NH-- and T is --OH or --Cl.